CN106684365A - Preparation of C-coated LiMn2O4 nanowire with high-temperature solid-state method - Google Patents

Preparation of C-coated LiMn2O4 nanowire with high-temperature solid-state method Download PDF

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Publication number
CN106684365A
CN106684365A CN201710059119.XA CN201710059119A CN106684365A CN 106684365 A CN106684365 A CN 106684365A CN 201710059119 A CN201710059119 A CN 201710059119A CN 106684365 A CN106684365 A CN 106684365A
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coating
nano wire
carbon
coated
manganese oxide
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郑鹏
刘婷
郭守武
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Preparation of a C-coated LiMn2O4 nanowire with a high-temperature solid-state method comprises the following steps: firstly, preparing a MnO nanowire precursor; secondly, placing glucose and the precursor in a hydrothermal reactor in proportion for a reaction at a certain temperature and coating a MnO nanowire with a C layer; finally, performing solid-state sintering on the MnO nanowire coated with the C layer and LiOH in proportion at a high temperature to obtain the C-coated LiMn2O4 nanowire. C-coated LiMn2O4 can be prepared, keeps nanowire morphology and has the characteristics of being simple to operate and low in cost.

Description

High temperature solid-state method prepares carbon coating LiMn2O4 nano wire
Technical field
The present invention relates to technical field of lithium ion battery positive pole material preparation, more particularly to a kind of high temperature solid-state method prepares carbon Cladding LiMn2O4 nano wire.
Background technology
LiMn2O4 (LiMn2O4) it is a kind of lithium electricity positive electrode, it has higher potential window, and raw material is cheap, times Rate performance and specific capacity are higher, in being successfully applied to lithium ion battery production.Traditional LiMn2O4It is solid through high temperature Prepared by phase method, pattern is all micron particle.Micron-scale is unfavorable for electronics and the quick diffusion transport of lithium ion.In order to further carry High its specific capacity, high rate performance and cyclical stability, can prepare the LiMn of nano-scale using nanotechnology2O4。
LiMn2O4With polyhedral structure, it is difficult to be prepared into one-dimensional nano line pattern.And one-dimensional nano structure is conducive to electricity Son transmission.In addition, high temperature solid-state can provide enough degree of crystallinity, be conducive to improving lithium electrical property, but, nano material often exists Reunite during experience high temperature solid-phase sintering, secondary length greatly micro materials have run counter to the preparation original intention of nano material.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of high temperature solid-state method prepares carbon bag LiMn2O4 nano wire is covered, the LiMn that surface is coated by carbon-coating can be prepared2O4, and LiMn2O4Nano wire pattern is kept, with behaviour The characteristics of making simple, with low cost.
In order to achieve the above object, the technical scheme taken of the present invention is：
High temperature solid-state method prepares carbon coating LiMn2O4 nano wire, and its step is as follows：
Step one：Prepare manganese oxide nanowire precursor；
Step 2：By glucose and presoma according to mass ratio 1：1 is placed in hydro-thermal axe, 2h is reacted at 180 DEG C, by carbon-coating It is coated on manganese oxide nanowire surface；
Step 3：The manganese oxide nano wire and Lithium hydrate of carbon-coating will be coated with according to mass ratio 2.05:1 in 500-750 Solid-phase sintering 1-5h under DEG C temperature conditionss, obtains carbon coating LiMn2O4 nano wire.
Material of the present invention has the beneficial effect that：
The inventive method can prepare the LiMn that surface is coated by carbon-coating2O4, and LiMn2O4Nano wire pattern can be kept, is received Rice noodle pattern can improve the electric conductivity of lithium electricity positive electrode, be conducive to improving lithium electrical property, and carbon coating layer can effectively suppress The dissolving of Mn, so as to improve LiMn2O4Cyclical stability.The LiMn produced using this method2O4As lithium electricity positive pole material Material, with repeatable strong, battery capacity is high and the characteristics of good rate capability.This method has simple to operate, with low cost Feature.
Description of the drawings
Fig. 1 is the XRD figure of the carbon coating LiMn2O4 nano wire prepared in embodiment one to four.Wherein, abscissa is angle； Vertical coordinate is relative intensity.
Fig. 2 is the SEM figures of the carbon coating LiMn2O4 nano wire prepared in embodiment one to four.
Fig. 3 is the XPS figures of the carbon coating LiMn2O4 nano wire prepared in embodiment one to four.
Fig. 4 is the charging and discharging curve figure of the carbon coating LiMn2O4 nano wire prepared in embodiment one to four.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Embodiment one
Step one：Take 1 part of manganese sulfate and 15 parts of potassium nitrate calcine 3h under 380 DEG C of air, before obtaining manganese oxide nano wire Drive body；
Step 2：0.01g glucoses and 0.01g presomas are placed in hydro-thermal axe, at 180 DEG C 2h is reacted, by carbon-coating bag Overlay on manganese oxide nanowire surface；
Step 3：The manganese oxide nano wire for being coated with carbon-coating by 2.05 parts and 1 part of Lithium hydrate are under 500 DEG C of temperature conditionss Solid-phase sintering 5h, obtains carbon coating LiMn2O4 nano wire.
Embodiment two
Step one：Take 1 part of manganese sulfate and 15 parts of potassium nitrate calcine 3h under 380 DEG C of air, before obtaining manganese oxide nano wire Drive body；
Step 2：0.1g glucoses and 0.1g presomas are placed in hydro-thermal axe, at 180 DEG C 2h is reacted, carbon-coating is coated In manganese oxide nanowire surface；
Step 3：The manganese oxide nano wire for being coated with carbon-coating by 2.05 parts and 1 part of Lithium hydrate are under 600 DEG C of temperature conditionss Solid-phase sintering 4h, obtains carbon coating LiMn2O4 nano wire.
Embodiment three
Step one：Take 1 part of manganese sulfate and 15 parts of potassium nitrate calcine 3h under 380 DEG C of air, before obtaining manganese oxide nano wire Drive body；
Step 2：2g glucoses and 2g presomas are placed in hydro-thermal axe, at 180 DEG C 2h is reacted, carbon-coating is coated on into oxygen Change manganese nanowire surface；
Step 3：The manganese oxide nano wire for being coated with carbon-coating by 2.05 parts and 1 part of Lithium hydrate are under 700 DEG C of temperature conditionss Solid-phase sintering 2h, obtains carbon coating LiMn2O4 nano wire.
Example IV
Step one：Take 1 part of manganese sulfate and 15 parts of potassium nitrate calcine 3h under 380 DEG C of air, before obtaining manganese oxide nano wire Drive body；
Step 2：10g glucoses and 10g presomas are placed in hydro-thermal axe, at 180 DEG C 2h is reacted, carbon-coating is coated on Manganese oxide nanowire surface；
Step 3：The manganese oxide nano wire for being coated with carbon-coating by 2.05 parts and 1 part of Lithium hydrate are under 750 DEG C of temperature conditionss Solid-phase sintering 2h, obtains carbon coating LiMn2O4 nano wire.
Referring to accompanying drawing 1, it is seen that carbon coating LiMn2O4 nano wire characteristic peak is indicated in such as figure, and at 20 ° Nearby there is the bulge at individual carbon peak, illustrate the LiMn2O4 for successfully synthesizing carbon coating.
Fig. 2 is the SEM figures of the carbon coating LiMn2O4 nano wire prepared in embodiment one to four.Can be clearly from Fig. 2 To the nano wire of a diameter of 50nm or so.
Fig. 3 is the XPS figures of the carbon coating LiMn2O4 nano wire prepared in embodiment one to four.Nanometer as can be seen from Figure 3 Line is made up of carbon, lithium, manganese and oxygen element.
Fig. 4 is the charging and discharging curve figure of the carbon coating LiMn2O4 nano wire prepared in embodiment one to four, under 0.2C, it Discharge capacity be up to 140mAh g-1。

Claims (5)

1. high temperature solid-state method prepares carbon coating LiMn2O4 nano wire, it is characterised in that step is as follows：
Step one：Prepare manganese oxide nanowire precursor；
Step 2：By glucose and presoma according to mass ratio 1：1 is placed in hydro-thermal axe, and at 180 DEG C 2h is reacted, and carbon-coating is coated In manganese oxide nanowire surface；
Step 3：The manganese oxide nano wire and Lithium hydrate of carbon-coating will be coated with according to mass ratio 2.05:1 in 500-750 DEG C of temperature Solid-phase sintering 1-5h under the conditions of degree, obtains carbon coating LiMn2O4 nano wire.
2. high temperature solid-state method according to claim 1 prepares carbon coating LiMn2O4 nano wire, it is characterised in that step is such as Under：
Step one：Take 1 part of manganese sulfate and 15 parts of potassium nitrate calcine 3h under 380 DEG C of air, obtain manganese oxide nanowire precursor；
Step 2：0.01g glucoses and 0.01g presomas are placed in hydro-thermal axe, at 180 DEG C 2h is reacted, carbon-coating is coated on Manganese oxide nanowire surface；
Step 3：The manganese oxide nano wire for being coated with carbon-coating by 2.05 parts and 1 part of Lithium hydrate solid phase under 500 DEG C of temperature conditionss Sintering 5h, obtains carbon coating LiMn2O4 nano wire.
3. high temperature solid-state method according to claim 1 prepares carbon coating LiMn2O4 nano wire, it is characterised in that step is such as Under：
Step one：Take 1 part of manganese sulfate and 15 parts of potassium nitrate calcine 3h under 380 DEG C of air, obtain manganese oxide nanowire precursor；
Step 2：0.1g glucoses and 0.1g presomas are placed in hydro-thermal axe, at 180 DEG C 2h is reacted, carbon-coating is coated on into oxygen Change manganese nanowire surface；
Step 3：The manganese oxide nano wire for being coated with carbon-coating by 2.05 parts and 1 part of Lithium hydrate solid phase under 600 DEG C of temperature conditionss Sintering 4h, obtains carbon coating LiMn2O4 nano wire.
4. high temperature solid-state method according to claim 1 prepares carbon coating LiMn2O4 nano wire, it is characterised in that step is such as Under：
Step one：Take 1 part of manganese sulfate and 15 parts of potassium nitrate calcine 3h under 380 DEG C of air, obtain manganese oxide nanowire precursor；
Step 2：2g glucoses and 2g presomas are placed in hydro-thermal axe, at 180 DEG C 2h is reacted, carbon-coating is coated on into manganese oxide Nanowire surface；
Step 3：The manganese oxide nano wire for being coated with carbon-coating by 2.05 parts and 1 part of Lithium hydrate solid phase under 700 DEG C of temperature conditionss Sintering 2h, obtains carbon coating LiMn2O4 nano wire.
5. high temperature solid-state method according to claim 1 prepares carbon coating LiMn2O4 nano wire, it is characterised in that step is such as Under：
Step one：Take 1 part of manganese sulfate and 15 parts of potassium nitrate calcine 3h under 380 DEG C of air, obtain manganese oxide nanowire precursor；
Step 2：10g glucoses and 10g presomas are placed in hydro-thermal axe, at 180 DEG C 2h is reacted, carbon-coating is coated on into oxidation Manganese nanowire surface；
Step 3：The manganese oxide nano wire for being coated with carbon-coating by 2.05 parts and 1 part of Lithium hydrate solid phase under 750 DEG C of temperature conditionss Sintering 2h, obtains carbon coating LiMn2O4 nano wire.
CN201710059119.XA 2017-01-23 2017-01-23 Preparation of C-coated LiMn2O4 nanowire with high-temperature solid-state method Pending CN106684365A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110189925A (en) * 2019-06-24 2019-08-30 安徽师范大学 The preparation method and application of one-dimensional manganese dioxide@carbon@nickel hydroxide core-shell structure copolymer nanowire composite

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008285372A (en) * 2007-05-18 2008-11-27 National Institute Of Advanced Industrial & Technology METHOD FOR MANUFACTURING SINGLE CRYSTAL LiMn2O4 NANOWIRE AND HIGH-RATE LITHIUM ION BATTERY USING THE SINGLE CRYSTAL LiMn2O4 NANOWIRE
CN102040249A (en) * 2010-12-02 2011-05-04 西安交通大学 Method for preparing lithium manganate nanowire made of positive material of lithium ion battery
CN102280634A (en) * 2011-07-05 2011-12-14 南开大学 Lithium manganese oxide electrode material with porous structure as well as manufacturing method and application thereof
CN103594695A (en) * 2012-08-13 2014-02-19 深圳华粤宝电池有限公司 Lithium ion battery cathode material lithium manganate and preparation method thereof
CN104022277A (en) * 2014-05-16 2014-09-03 武汉理工大学 Li2MnO3 nanowire, preparation method and application thereof
CN104176783A (en) * 2014-08-15 2014-12-03 东南大学 Preparation method and application method for nitrogen-carbon-material-coated manganese dioxide nanowire
CN105261743A (en) * 2015-09-06 2016-01-20 武汉科技大学 Carbon-coated vanadium trioxide nanowire thin film with pod structure and preparation method of carbon-coated vanadium trioxide nanowire thin film with pod structure
CN106252622A (en) * 2016-08-23 2016-12-21 深圳市贝特瑞新能源材料股份有限公司 A kind of silicon oxide/carbon composite nano line negative material, preparation method and lithium ion battery

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008285372A (en) * 2007-05-18 2008-11-27 National Institute Of Advanced Industrial & Technology METHOD FOR MANUFACTURING SINGLE CRYSTAL LiMn2O4 NANOWIRE AND HIGH-RATE LITHIUM ION BATTERY USING THE SINGLE CRYSTAL LiMn2O4 NANOWIRE
CN102040249A (en) * 2010-12-02 2011-05-04 西安交通大学 Method for preparing lithium manganate nanowire made of positive material of lithium ion battery
CN102280634A (en) * 2011-07-05 2011-12-14 南开大学 Lithium manganese oxide electrode material with porous structure as well as manufacturing method and application thereof
CN103594695A (en) * 2012-08-13 2014-02-19 深圳华粤宝电池有限公司 Lithium ion battery cathode material lithium manganate and preparation method thereof
CN104022277A (en) * 2014-05-16 2014-09-03 武汉理工大学 Li2MnO3 nanowire, preparation method and application thereof
CN104176783A (en) * 2014-08-15 2014-12-03 东南大学 Preparation method and application method for nitrogen-carbon-material-coated manganese dioxide nanowire
CN105261743A (en) * 2015-09-06 2016-01-20 武汉科技大学 Carbon-coated vanadium trioxide nanowire thin film with pod structure and preparation method of carbon-coated vanadium trioxide nanowire thin film with pod structure
CN106252622A (en) * 2016-08-23 2016-12-21 深圳市贝特瑞新能源材料股份有限公司 A kind of silicon oxide/carbon composite nano line negative material, preparation method and lithium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WEIWEI SUN等: "A general strategy to construct uniform carbon-coated spinel LiMn2O4 nanowires for ultrafast rechargeable lithium-ion batteries with a long cycle life", 《NANOSCALE》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110189925A (en) * 2019-06-24 2019-08-30 安徽师范大学 The preparation method and application of one-dimensional manganese dioxide@carbon@nickel hydroxide core-shell structure copolymer nanowire composite
CN110189925B (en) * 2019-06-24 2021-09-28 安徽师范大学 Preparation method and application of one-dimensional manganese dioxide @ carbon @ nickel hydroxide core-shell nanowire composite material

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